CN107868342A - One kind exempts from spray coating polypropylene composition and preparation method thereof - Google Patents
One kind exempts from spray coating polypropylene composition and preparation method thereof Download PDFInfo
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- CN107868342A CN107868342A CN201711008207.3A CN201711008207A CN107868342A CN 107868342 A CN107868342 A CN 107868342A CN 201711008207 A CN201711008207 A CN 201711008207A CN 107868342 A CN107868342 A CN 107868342A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses one kind to exempt from spray coating polypropylene composition, it is characterised in that：By weight, comprising following components：40 parts ~ 98 parts of acrylic resin；0.5 part ~ 3 parts of effect pigment；Wherein, the effect pigment by weight, including following components：Low 60 parts ~ 100 parts of radius-thickness ratio aluminium powder；High 0 part ~ 40 parts of radius-thickness ratio aluminium powder；0 part ~ 40 parts of pearl essence.The present invention can be improved, make material has excellent integrated appearance effect by the aluminium powder of the low radius-thickness ratio from particular range from material angle to material；And the pearl essence of high radius-thickness ratio aluminium powder or specified particle diameter by compounding a small amount of particular range, what is be prepared exempts from spray coating polypropylene composition and material can more preferably be improved from material angle, and make material has more excellent integrated appearance effect.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of to exempt from spray coating polypropylene group with aesthetic appearance
Compound and preparation method thereof.
Background technology
Polypropylene PP, hemicrystalline plastics, have the characteristics that density is low, easy processing, it has also become dosage is most in auto plasticses
Big kind.But polypropylene surface can be low, spray painting is difficult, the polypropylene surface pre-treatment with reference to complexity is needed before spray painting, simultaneously
The fraction defective that paints is high, and the influence of health and environment to people is big.
The B of Chinese patent CN 103112096 use installs ultrasonic equipment additional at extruding dies, improves polyester and aluminium powder
Affinity, so as to lower the current mark and weld bond problem in injection molding process；The B of Chinese patent CN 103910941 pass through
Using compatibilization techniques, by filler and polarity compatible dosage form into cross-linked network structure, pigment distribution is sent out with melt flows
The behavior for changing is restricted, so as to reduce weld bond and current mark defect；The B of Chinese patent CN 102643505 are using tool
Magnetic metallic pigments master batch method, by the externally-applied magnetic field in shaping, the orientations of metallic pigments is controlled so as to reduce welding
Line and current mark.
But in method disclosed in above-mentioned patent, by adding the means of ultrasonic wave and additional compatilizer, belong to limitation
The upset of effect pigment in forming process, but this limitation is extremely limited, it is difficult to reach and really eliminate current mark and weld bond
Defect, while the requirement to injection molding process is very high.And the method by adding magnetic master batch, the optional effect face of master batch
Material limits to very much, while requires that former has the function of externally-applied magnetic field.Therefore still need a kind of preparation technology of exploitation for this area
It is simple and exempt from spray coating polypropylene material to moulding process and mould are less demanding, so as to more can be suitably used for inner and outer decorative parts of automobile or
The other application such as household electrical appliances field.
The content of the invention
For overcome the deficiencies in the prior art or defect, primary and foremost purpose of the invention is that provide one kind gathers with spraying is exempted from
Propylene compositions, said composition can obtain high metal-like, and the weld bond and current mark defect in forming process are had
Effect improves, and welding line strength has clear improvement, and exempts from sprayed product to mold design and moulding process so as to advantageously reduce
It is required that.
Another object of the present invention is to provide the above-mentioned preparation method for exempting from spray coating polypropylene composition.
The present invention is to be achieved through the following technical solutions：
One kind exempts from spray coating polypropylene composition, by weight, includes following components：
40 parts ~ 98 parts of acrylic resin；
0.5 part ~ 3 parts of effect pigment；
Wherein, the effect pigment by weight, including following components：
Low 60 parts ~ 100 parts of radius-thickness ratio aluminium powder；
High 0 part ~ 40 parts of radius-thickness ratio aluminium powder；
0 part ~ 40 parts of pearl essence.
Wherein, the low radius-thickness ratio aluminium powder is silver dollar type, and average grain diameter D50 is 30 μm ~ 100 μm, and radius-thickness ratio is 6 ~ 15,
Preferably 8 ~ 12；When radius-thickness ratio is too low, covering power is too poor, and addition is high, and metal sense is bad；When radius-thickness ratio is too high, resistant to shearing energy
Power is deteriorated, and aluminium flake is easily overturn with stream, causes current mark and weld bond serious.
Wherein, the radius-thickness ratio refers to the ratio of diameter and thickness, the method for testing of the radius-thickness ratio：Separated and dissolved first
Go out corresponding effect pigment, analyzed by electron microscope；Then sample is molded into square plate, cuts sample, penetrated by X
Line three-dimensional microscope carries out the pattern of lossless viewed in transmittance aluminium flake, is measured with electron microscope amplification.
Wherein, the high radius-thickness ratio aluminium powder is silver dollar type, and average grain diameter D50 is 10 μm ~ 100 μm, and radius-thickness ratio is 16 ~ 30,
Preferably 18 ~ 25.
Wherein, the particle size range of the pearl essence is 10 μm ~ 300 μm.
Wherein, the acrylic resin is acrylic resin copolymer, the melt quality stream under 230 DEG C, 2.16 Kg loads
Dynamic speed MFR is the g/10min of 30 g/10min~100.
In addition, above-mentioned exempt from spray coating polypropylene composition, can also include：0 ~ 25 part of toughener, 0 ~ 25 part of filler, 0 ~ 2 part
Auxiliary agent；The toughener is selected from polyolefin elastomer, hydrogenated styrene-butadiene block copolymer SEBS, ethylene-propylene-diene monomer
One or more in glue EPDM；One kind in talcum powder, calcium carbonate, wollastonite, whisker, glass fibre of the filler or
It is several；One or more of the auxiliary agent in antioxidant, light stabilizer, lubricant.
Wherein, the antioxidant is Hinered phenols and/or phosphite ester kind antioxidant, preferably antioxidant 1010, antioxygen
One or more in agent 1076, antioxidant 3114, irgasfos 168, phosphite ester PEP-36；The light stabilizer is hindered amine
Class light stabilizer, preferably light stabilizer 3808（UV-3808PP5）, piperidines stearate（LA-402XP、LA-402AF）In
It is one or more of；The lubricant is in silicone, esters, amide-type, polyethylene kind, stearic acid, aliphatic acid and esters
One or more.
The above-mentioned preparation method for exempting from spray coating polypropylene composition, comprises the following steps：
Acrylic resin, effect pigment, toughener, filler and auxiliary agent are weighed according to proportioning to carry out after being well mixed, and add double spiral shells
In bar extruder, carry out melting mixing, melting mixing temperature be 170 DEG C ~ 220 DEG C, screw speed be 350 revs/min ~ 450 turns/
Point, extruding pelletization, obtain exempting from spray coating polypropylene composition.
The present invention compared with prior art, has the advantages that：
1）The present invention can be improved to material from material angle, be made by the aluminium powder of the low radius-thickness ratio from particular range
Material has excellent integrated appearance effect, is embodied in the molded appearance defects such as current mark, weld bond and multi-angle aberration
It is decreased obviously, while there is high welding line strength and good metal appearance.It is in addition, thick by the low footpath from particular range
The aluminium powder of ratio compounds the pearl essence of high the radius-thickness ratio aluminium powder or specified particle diameter of a small amount of particular range, can be from material angle to material
Material is more preferably improved, and make material has more excellent integrated appearance effect, is embodied in current mark, weld bond and polygonal
The molded appearance defects such as degree aberration are decreased obviously, while have high welding line strength and good metal appearance.
2）The preparation technology of the present invention is simple, to the less demanding of mold design and moulding process, can be applied to structure compared with
For the product of complexity, the application field for exempting from sprayed product has been widened；It can also be applied to prepare inner and outer decorative parts of automobile and family simultaneously
The field such as electricity product, there is the aesthetic effect of similar spraying.
Embodiment
The present invention is further illustrated below by embodiment, following examples are the preferable embodiment party of the present invention
Formula, but embodiments of the present invention are not limited by following embodiments.
The testing standard or method of each performance indications：
Average grain diameter D50：The cumulative particle sizes percentile of one sample reaches particle diameter corresponding when 50%.Its physics meaning
Justice is that particle diameter accounts for 50% more than its particle, and also accounting for 50%, D50 less than its particle is also median or median particle diameter, can be with
Tested with Malvern Particle Size Analyzer.
Radius-thickness ratio：Separated and dissolved goes out corresponding effect pigment first, is analyzed by electron microscope；Then by sample
Square plate is molded into, cuts sample, the pattern of lossless viewed in transmittance aluminium flake is carried out by X ray three-dimensional microscope, uses electron microscopic
Mirror amplification measures.
Integrated appearance efficiency index E：Exempt from the integrated appearance effect of sprayed product, comprehensive every test index number for evaluating
According to providing efficiency index defined formula, wherein S represents metal sense effect, T（WD）Welding line strength is represented,
V represents the visibility of weld bond and current mark, and L represents welding line length.
The visibility V of weld bond and current mark：By particular mold, hole is opened up in structure, observes weld bond and stream
The visibility V of trace（1 grade：Almost without weld bond and current mark, 2 grades：Acceptable faint weld bond and current mark, 3 grades：It is more apparent
Weld bond and current mark, 4 grades：Obvious weld bond and current mark）.
Welding line length L：By mould, hole is opened up in structure, by using the visual weld bond of kind of calliper from
The length to be extended out at hole.
Welding line strength T（WD）：Cast gate is opened up from both ends using ISO tensile bars, stream convergence is formed among batten,
Tested according to ISO 527.
Metal sense S：Judged by vision（0 grade：Almost without metal sense；1 grade：Metal sense is slightly weak；2 grades：Moderate metal sense；3
Level：Strong metal sense）.
Embodiments of the invention and comparative example use the following raw material, but are not limited only to these raw materials：
Acrylic resin：COPP, the melt mass flow rate MFR under 230 DEG C, 2.16 Kg loads are 70 g/
10min, producer are Exxon Mobil；
Effect pigment：Low radius-thickness ratio aluminium powder -1：Silver dollar type, average grain diameter D50 are 35 μm, radius-thickness ratio 10；
Low radius-thickness ratio aluminium powder -2：Silver dollar type, average grain diameter D50 are 35 μm, radius-thickness ratio 6；
Low radius-thickness ratio aluminium powder -3：Silver dollar type, average grain diameter D50 are 35 μm, radius-thickness ratio 15；
Low radius-thickness ratio aluminium powder -4：Silver dollar type, average grain diameter D50 are 35 μm, radius-thickness ratio 3；
High radius-thickness ratio aluminium powder -1：Silver dollar type, average grain diameter D50 are 35 μm, radius-thickness ratio 22；
High radius-thickness ratio aluminium powder -2：Silver dollar type, average grain diameter D50 are 35 μm, radius-thickness ratio 16；
High radius-thickness ratio aluminium powder -3：Silver dollar type, average grain diameter D50 are 35 μm, radius-thickness ratio 30；
High radius-thickness ratio aluminium powder -4：Silver dollar type, average grain diameter D50 are 35 μm, radius-thickness ratio 35；
Pearl essence, particle size range are 20 μm ~ 60 μm；
Toughener：Polyolefin elastomer, producer are DOW Chemical；
Filler：Talcum powder, producer are to add source chemical industry；
Auxiliary agent：Antioxidant：Antioxidant 1010, producer are three Feng Huagong；
Irgasfos 168, producer are three Feng Huagong；
Light stabilizer：Light stabilizer 3808（UV-3808PP5）, producer is that cyanogen is special；
Lubricant：Zinc stearate, producer are Zhongshan Belike Chemical Materials Technology Co., Ltd..
Embodiment 1-12 and comparative example 1-9：Exempt from the preparation of spray coating polypropylene composition
Acrylic resin, effect pigment, toughener, filler and auxiliary agent are carried out after being well mixed according to the proportioning of table 1, added double
In screw extruder, carry out melting mixing, melting mixing temperature be 170 DEG C ~ 220 DEG C, screw speed be 350 revs/min ~ 450 turns/
Point, extruding pelletization, obtain exempting from spray coating polypropylene composition.What is be prepared exempts from the integrated appearance index of spray coating polypropylene composition
Evaluation result is as shown in table 1, while encloses the visibility of weld bond and current mark, welding line length, welding line strength, metal sense
Deng related test parameters data.
The embodiment 1-12 of table 1 and comparative example 1-9 each group distribution ratio（Parts by weight）And each the performance test results
Continued 1
。
Claims (8)
1. one kind exempts from spray coating polypropylene composition, it is characterised in that：By weight, comprising following components：
40 parts ~ 98 parts of acrylic resin；
0.5 part ~ 3 parts of effect pigment；
Wherein, the effect pigment by weight, including following components：
Low 60 parts ~ 100 parts of radius-thickness ratio aluminium powder；
High 0 part ~ 40 parts of radius-thickness ratio aluminium powder；
0 part ~ 40 parts of pearl essence.
2. according to claim 1 exempt from spray coating polypropylene composition, it is characterised in that：The low radius-thickness ratio aluminium powder is silver dollar
Type, average grain diameter D50 are 30 μm ~ 100 μm, and radius-thickness ratio is 6 ~ 15, preferably 8 ~ 12.
3. according to claim 1 exempt from spray coating polypropylene composition, it is characterised in that：The high radius-thickness ratio aluminium powder is silver dollar
Type, average grain diameter D50 are 10 μm ~ 100 μm, and radius-thickness ratio is 16 ~ 30, preferably 18 ~ 25.
4. according to claim 1 exempt from spray coating polypropylene composition, it is characterised in that：The particle size range of the pearl essence is
10μm ~300μm。
5. according to claim 1 exempt from spray coating polypropylene composition, it is characterised in that：The acrylic resin is poly- for copolymerization
Allyl resin, melt mass flow rate MFR under 230 DEG C, 2.16 Kg loads are the g/10min of 30 g/10min~100.
6. according to claim 5 exempt from spray coating polypropylene composition, it is characterised in that：Also include：0 ~ 25 part of toughener, 0 ~
25 parts of fillers, 0 ~ 2 part of auxiliary agent；The toughener is selected from polyolefin elastomer, hydrogenated styrene-butadiene block copolymer
One or more in SEBS, ethylene propylene diene rubber EPDM；The filler is selected from talcum powder, calcium carbonate, wollastonite, whisker, glass
One or more in glass fiber；One or more of the auxiliary agent in antioxidant, light stabilizer, lubricant.
7. according to claim 6 exempt from spray coating polypropylene composition, it is characterised in that：The antioxidant is Hinered phenols
And/or phosphite ester kind antioxidant, preferably antioxidant 1010, antioxidant 1076, antioxidant 3114, irgasfos 168, phosphorous acid
One or more in ester PEP-36；The light stabilizer is hindered amine light stabilizer, preferably light stabilizer 3808, piperidines
One or more in stearate；The lubricant is selected from silicone, esters, amide-type, polyethylene kind, stearic acid, fat
One or more in fat acid and esters.
A kind of 8. preparation method for exempting from spray coating polypropylene composition as described in claim any one of 1-7, it is characterised in that：Bag
Include following steps：
Acrylic resin, effect pigment, toughener, filler and auxiliary agent are weighed according to proportioning to carry out after being well mixed, and add double spiral shells
In bar extruder, carry out melting mixing, melting mixing temperature be 170 DEG C ~ 220 DEG C, screw speed be 350 revs/min ~ 450 turns/
Point, extruding pelletization, obtain exempting from spray coating polypropylene composition.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711008207.3A CN107868342B (en) | 2017-10-25 | 2017-10-25 | Spraying-free polypropylene composition and preparation method thereof |
| PCT/CN2018/100320 WO2019080608A1 (en) | 2017-10-25 | 2018-08-14 | Spraying-free polypropylene composition and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711008207.3A CN107868342B (en) | 2017-10-25 | 2017-10-25 | Spraying-free polypropylene composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107868342A true CN107868342A (en) | 2018-04-03 |
| CN107868342B CN107868342B (en) | 2020-02-14 |
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| CN201711008207.3A Active CN107868342B (en) | 2017-10-25 | 2017-10-25 | Spraying-free polypropylene composition and preparation method thereof |
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|---|---|
| CN (1) | CN107868342B (en) |
| WO (1) | WO2019080608A1 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707279A (en) * | 2018-05-18 | 2018-10-26 | 中广核俊尔（上海）新材料有限公司 | A kind of eutectic lapping defect exempts from spray coating polypropylene composite material and preparation method without current mark |
| CN109679209A (en) * | 2018-12-25 | 2019-04-26 | 重庆科聚孚工程塑料有限责任公司 | The PP composite material and preparation method of metal-like |
| CN111138764A (en) * | 2020-01-03 | 2020-05-12 | 江苏吉麦新能源车业有限公司 | Polypropylene plate free of metallic color coating and preparation method thereof |
| CN113881142A (en) * | 2021-11-05 | 2022-01-04 | 深圳市捷创新材料股份有限公司 | Green and environment-friendly spraying-free skin-like PP (polypropylene) modified material and preparation method thereof |
| CN113930018A (en) * | 2021-11-08 | 2022-01-14 | 青岛国恩科技股份有限公司 | Spraying-free composite material for vehicle and preparation method thereof |
| CN114249942A (en) * | 2021-03-04 | 2022-03-29 | 东莞市久磐塑胶有限公司 | Spraying-free flame-retardant uv-resistant plastic, production equipment and processing method |
| CN114685893A (en) * | 2022-03-31 | 2022-07-01 | 金发科技股份有限公司 | Low-density and good-mechanical-property spray-free polypropylene composition and preparation method and application thereof |
| CN114752176A (en) * | 2022-03-17 | 2022-07-15 | 金发科技股份有限公司 | Spraying-free resin and preparation method and application thereof |
| CN114752135A (en) * | 2022-03-09 | 2022-07-15 | 金发科技股份有限公司 | Rotational molding polyethylene material free of metal spraying effect and preparation method and application thereof |
| US11884793B2 (en) | 2019-10-30 | 2024-01-30 | The Procter & Gamble Company | Molded article with metallic appearance |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707279A (en) * | 2018-05-18 | 2018-10-26 | 中广核俊尔（上海）新材料有限公司 | A kind of eutectic lapping defect exempts from spray coating polypropylene composite material and preparation method without current mark |
| CN108707279B (en) * | 2018-05-18 | 2021-01-19 | 中广核俊尔（上海）新材料有限公司 | Low-melting-mark flow-mark-free spraying-free polypropylene composite material and preparation method thereof |
| CN109679209A (en) * | 2018-12-25 | 2019-04-26 | 重庆科聚孚工程塑料有限责任公司 | The PP composite material and preparation method of metal-like |
| US11884793B2 (en) | 2019-10-30 | 2024-01-30 | The Procter & Gamble Company | Molded article with metallic appearance |
| CN111138764A (en) * | 2020-01-03 | 2020-05-12 | 江苏吉麦新能源车业有限公司 | Polypropylene plate free of metallic color coating and preparation method thereof |
| CN114249942A (en) * | 2021-03-04 | 2022-03-29 | 东莞市久磐塑胶有限公司 | Spraying-free flame-retardant uv-resistant plastic, production equipment and processing method |
| CN113881142A (en) * | 2021-11-05 | 2022-01-04 | 深圳市捷创新材料股份有限公司 | Green and environment-friendly spraying-free skin-like PP (polypropylene) modified material and preparation method thereof |
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| CN114752176B (en) * | 2022-03-17 | 2023-10-31 | 金发科技股份有限公司 | Spraying-free resin and preparation method and application thereof |
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| Publication number | Publication date |
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| CN107868342B (en) | 2020-02-14 |
| WO2019080608A1 (en) | 2019-05-02 |
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